Extract containing unsaturated and aromatic hydrocarbons



Patented Nov. 5, 1940 UNITED STATES PATENT orl-" ca I EXTRACT CONTAINING UNSATURATED AND AROMATIC HYDROCARBONS Arthur Lazar, Berkeley, Calif., assignor to Tide Water Associated Oil Compa y, San Francisco, Calii'., a corporation of Delaware No Drawing. Application March 22, 1988,

- Serial No. 197,407

' 8Claims. (Cl. 196-149) larly when within determinable viscosity ranges.

In treating petroleum, or its distillates, with such selective solvents, the solvents take up cer- 15 tain hydrocarbons which may generally be termed unsaturated and aromatic hydrocarbons and which, when in solution, are removed as an extract from the main body of oil under treatment. These extracted hydrocarbons are then 20 separated from the selective solvent used, which latter is used over and over again, but up to the present time very limited use has been found for such extracted hydrocarbons, partly due to their composition and partly because they possess very 25 undesirable features, such as dark color, strong fluorescence and instability against light.

Treatment with sulphuric acid in the usual way will not change these conditions to any marked degree, because in order to obtain any 30 appreciable effect as to decolorizing and color stability such tremendous quantities of sulphuric acid must be used that a large portion of the extract will be converted into valueless acid sludge. Even when such a severe acid treatment is given 85 the extract, the oil remaining after removal of acid sludge does not. show features desirable for use in the many applications which this invention now provides. I

In order to purify the extract to obtain lighter '40 and permanent color, it is found that such may be accomplished in general by distilling the,

50 tillation step, either of which may be used to,

obtain the desired results. The first method consists in agitating the alkaline reagent with the extract, then removing the excess alkali together with whatever precipitate 55 that may have been formed and distilling the treated extract in the usual manner to obtain a condensate, or the extract may be distilled under high vacuum with direct steam without removal of the alkaline material to leave from 10% to 20% of bottoms.

In the event that such excess alkali and precipitate is removed there will be no alkali dissolved in the oil when the original extract contains no organic acidic compounds, such as naphthenic acids, but any alkali contained therein will be in suspension.

However, if the original extract, or original distillate from which such extract is derived contains such organic acidic compounds, the tendency is to form oil soluble organic salts or soaps.

In either event like valuable products are obtained to be used as resin oil substitutes but the bottoms after redistillation have difierent properties; the bottoms from an extract containing organic acidic compounds contain valuable oilsoluble soaps, such as soaps of naphthenic acid and sulphonated naphthenic acids which have a pronounced emulsifying eifect in contact with water, or impart such emulsifying eflects when added to ordinary mineral oils. 5

0n the other hand, the bottoms from an extract containing no organic acidic compounds will be free from soaps and contain largely mineral salts which do not have this emulsifying property.

These emulsifiable products are claimed in my copending application, Serial Number 82,549 filed May 29, 1936, of which this application is a continuaticn-in-part;

The second method consists in treating the extract with sulphuric acid in such quantity that it exercises no chemical effect on the oil itself, but Just coagulates the resinous bodies. The point at which the coagulation of the resinous bodies is complete and a further addition of acid 40 would have a noticeable chemical effect on the oil itself, is indicated by a liberation of S02 gas during the agitation. The amount of sulphuric acid necessary and the strength of the sulphuric acid which 'will bring about this desired efiect varies within certain limits depending on the nature of the extract which again varies with the source of crude from which the oil originated. It has been found that acid rates can vary between one and ten pounds per barrel of extract and that the strength of sulphuric acid can vary between 90% and 98%. The variations in the nature of the extracts will be easily understood from the fact that the various solvents used for refining differ from each other quite considerably in their selectivity and that the crude 'distillates on which the solventsare applied differ quite I considerably in their composition.

The acid sludge is then separated from the oil which is-neutralized by the ordinary use of adsorbent material, such as filtration through day. Alternatively the acid treated extract, after sludge removal, may be distilled under high vacuum with direct steam in the presence of the alkaline material and the oil recovered as a desired condensate, leaving from to 20% of bottoms. The efiect of the alkaline reagents used is to insure a substantially complete removal of compounds of an acidic nature together with the destruction, or polymerization, of certain unstable compounds left in the oil. It would seem that the removal, or separation, of the above compounds removes the causes for re-' Example A An extract containing unsaturated and aromatic hydrocarbons obtained from treating a California lubricating distillate, or any other lubricating crude oil with liquid S02, being free from organic acidic compounds and having an approximate range of viscosity between 40 S. U. at 100 F. and 150 S. U. at 210 F., is agitated for about one hour with concentrated sulphuric 40 acid (98%) at atmospheric temperature, the acid being used-at the rate of about two pounds of acid per barrel of extract. The mixture is then permitted to settle for about twelve hours and the acid sludge is then removed. The acid treated extract is redistilled (preferably under vacuum) in the presence of from 0.8 to 1.0 pounds of NaOH per barrel of the extract to recover the desired resin oil substitutes, which may be fractionated to yield a light resin oil substitute comprising about 10% of the' charge, a medium resin oil substitute comprising about 40% of the charge and a heavy resin oil substitute comprising about 40% of the charge, thus leaving about 10% of bottoms. In this case the bottoms contain besides residual oily constituents an appreciable Example B An extract containing unsaturated and aromatic hydrocarbons obtained from treating a California lubricating distillate, or any other lubricating crude oil, with liquid S02, containing organic acids and having an approximate range of viscosity between 40 S. U. at F. and S. U. at 210 F., is agitated for about one hour with concentrated sulphuric acid (98%) at atmospheric temperature, the acid being used at the rate of about 2 pounds of acid per barrel '55- of extract.:.- The mixture .is then permitted to oily constituents an appreciable quantity of oil soluble soaps of organic acids and of sulfonated organic acids together with the salts of what-- ever other products of acid nature which have been imparted to the oil by the action of the acid. The bottoms thus obtained from the treatment by Example B have valuable emulsifying properties with water and emulsions may be made therefrom by dispersal in desired volumes of water or by, diluting with further mineral oil and dispersing the dilution in water.

The extract, or resin oil substitutes, processed as above described, shows excellent compatibility with solvents like alcohol, acetone, esters, and other organic compounds, a property which ordinary mineral oil does not possess. Furthermore, the treated extract is a desirable plasticiser for nitrocellulose lacquers and enamels being of a non-drying viscous character and very stable in the presence of light.

The extract may also be used as a solvent for rubber, either alone, or mixed in any proportion with other rubber solvents, as a substitute for refined resin oils, and generally'as a solvent for resins, gums, varnishes or asphalt.

Likewise, the extract has a wide field as a blending material with all vegetable oils, particularly castor oil, a property which ordinary hydrocarbon oils do not possess.

The extract processed as above, has valuable and unique properties which distinguish it clearly from ordinary mineral oils.

Applicant's product has all the valuable characteristics of refined resin oils, particularly as to high solvency for and compatibility with numerous orgarfic substances, without having the objectionable features of resin oils such as instability to oxygen and light, tendency to drying, and content of saponifiable material.

The following table gives a more detailed comparison of .the characteristics of applicant's new product with ordinary mineral and refined resin oil:

It will be noted that the evolution of S0: from the treatment with sulphuric acid is merely indicative oi the amount of sulphuric acid which should be used, and the amount of sulphuric acid which should be used, and the amount and concentration of the acid used is such as to cause substantially no oxidation or sulphonation of the extracted hydrocarbons.

In the appended claims the term unsaturated is applied to denote hydrocarbons containing one or more double or triple bonds not within an aromatic nucleus.

This application is a continuation-in-part of my copending application, Serial Number 82,549, filed May 29, 1936, which is a continuation-inpart of copending application Serial Number 723,168, filed April 30, 1934, which latter is a continuation-in-part of Serial Number 492,613, filed October 31, 1930.

I claim:

1. As an article of manufacture: a solvent extract of aromatic and unsaturated character from an uncracked petroleum oil distillate heavier than kerosene, said extract being soluble in liquid sulphur dioxide and substantially free oi constituents polymerizable by distillation in the presence of caustic soda and containing constituents reactable with a to 98% sulphuric acid when applied at a rate in excess of ten pounds per barrel.

2. An article according to claim 1 which has a specific gravity of about 0.965.

3. An article according to claim 1 which has a specific gravity of about 0.965 and which is soluble in alcohol, acetone, and castor oil.

4. An article according to claim 1 which has a viscosity between 40 sec. S. U. at 100 F. and sec. S. U. at 210 F.

5. An article according to claim 1 which has a viscosity between 40 sec. S. U. at 100 F. and 150 sec. S. U. at 210" F., and which has a refractive index of about 1.54 and substantially no saponification value.

6. An article according to claim 1 which has a specific gravity between 0.96 and 0.99, a Saybolt Universal viscosity between 40 seconds at 100 F. and 150 seconds at 210 F., and substantially no tendency to dry when exposed in thin films.

7. As an article of manufacture: a solvent extract of aromatic and unsaturated character from an uncracked petroleum oil distillate heavier than kerosene, said extract being soluble in liquid sulphur dioxide and substantially free of constituents polymerizable by distillation in the presence of caustic soda while containing constituents reactable with a 90 to 98% sulphuric acid when applied at a rate in excess of two pounds per barrel.

8. As an article of manufacture: a solvent extract of aromatic and. unsaturated character from an uncracked petroleum oil distillate heavier than kerosene, said extract being soluble in liquid sulphur dioxide and substantially free of constituents polymerizable by distillation in the presence of caustic soda while containing constituents reactable with a 90 to 98% sulphuric acid when applied at atmospheric temperature at a rate in excess of ten pounds per barrel.

' ARTHUR L'AZAR. 

